Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles

doi:10.1007/s11706-016-0334-z

Front. Mater. Sci.

2016, Vol. 10

Issue (2) : 178-186 https://doi.org/10.1007/s11706-016-0334-z

RESEARCH ARTICLE

Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles

Junbo LI^1,^*(

),Jianlong ZHAO²,Wenlan WU²,Ju LIANG¹,Jinwu GUO¹,Huiyun ZHOU¹,Lijuan LIANG¹

1. College of Chemical Engineering & Pharmaceutics, Henan University of Science & Technology, Luoyang 471023, China
2. Medical School, Henan University of Science & Technology, Luoyang 471003, China

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Abstract

In this paper, double hydrophilic ionic liquid block copolymers (ILBCs), poly poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine)]-block-(N-isopropylacrylamide) (PMMPImB-b-PNIPAAm) was first synthesized by reversible addition-fragmentation chain transfer (RAFT) and then attached on the surface of gold nanoparticles (Au NPs) via a strong gold-sulfur bonding for preparing hybrid nanoparticles (PMMPImB-b-PNIPAAm-@-Au NPs). The hybrid NPs had a three layers micelle-like structure, including a gold core, thermo-responsive inner shell and anion responsive outer corona. The self-assembling behavior of thermal- and anion-response from shell and corona were respectively investigated by change of temperature and addition of (CF₃SO₂)₂N^-. The results showed the hybrid NPs retained a stable dispersion beyond the lower critical solution temperature (LCST) because of the space or electrostatic protecting by outer PMMPImB. However, with increasing concentration of (CF₃SO₂)₂N^-, the micellization of self-assembling PMMPImB-b-PNIPAAm-@-Au NPs was induced to form micellar structure containing the core with hydrophobic PMMPImB-(CF₃SO₂)₂N^- surrounded by composite shell of Au NPs-PNIPAAm via the anion-responsive properties of ILBCs. These results indicated that the block copolymers protected plasmonic nanoparticles remain self-assembling properties of block copolymers when phase transition from outer corona polymer.

Keywords block?copolymer dual stimuli-responsive gold nanoparticles (Au NPs) self-assembly

Corresponding Author(s): Junbo LI

Online First Date: 05 April 2016 Issue Date: 11 May 2016

Cite this article:

Junbo LI,Jianlong ZHAO,Wenlan WU, et al. Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles[J]. Front. Mater. Sci., 2016, 10(2): 178-186.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-016-0334-z
https://academic.hep.com.cn/foms/EN/Y2016/V10/I2/178

Fig.1 Scheme 1The schematic representation of preparing PMMPImB-b-PNIPAAm-Au NPs and its temperature and anion responsive self-assembly.

Fig.2 Scheme 2The schematic representation for synthesis of PMMPImB-CTA and PMMPImB-b-PNIPAAm.

Fig.3 ¹HNMR spectra of (A) PMMPImB-CTA and (B) PMMPImB-b-PNIPAAm in DMSO.

Fig.4 GPC traces of PMMPImB-CTA (A) and PMMPImB-b-PNIPAAm (B) in 8.5 g/L NaNO₃ aqueous solution at room temperature.

Fig.5 (A) UV-vis spectrum, (B) TEM image and (C) DLS of PMMPImB-b-PNIPAAm-@-Au NPs. (D) TGA analysis of PMMPImB-b-PNIPAAm (a) and PMMPImB-b-PNIPAAm-@-Au NPs (b).

Fig.6 (A) The SPR peak and (B) responses of transmittance as a function of the concentration of (CF₃SO₂)₂N^- of PMMPImB-b-PNIPAAm-@-Au NPs. (C) The DLS result and (D) TEM image of the hybrid micelles solution forming at 0.2 mmol/L (CF₃SO₂)₂N^-.

Fig.7 (A) The SPR peak and (B) responses of transmittance of PMMPImB-b-PNIPAAm-@-Au NPs as a function of the temperature. (C) The DLS result and (D) TEM image of the PMMPImB-b-PNIPAAm-@-Au NPs at 42°C.

1	Chen Q, Ke H, Dai Z, . Nanoscale theranostics for physical stimulus-responsive cancer therapies. Biomaterials, 2015, 73: 214–230
2	Garanger E, MacEwan S R, Sandre O, . Structural evolution of a stimulus-responsive diblock polypeptide micelle by temperature tunable compaction of its core. Macromolecules, 2015, 48(18): 6617–6627
3	Hill M R, MacKrell E J, Forsthoefel C P, . Biodegradable and pH-responsive nanoparticles designed for site-specific delivery in agriculture. Biomacromolecules, 2015, 16(4): 1276–1282
4	Lehto J, Vaaramaa K, Vesterinen E, . Uptake of zinc, nickel, and chromium by N-isopropyl acrylamide polymer gels. Journal of Applied Polymer Science, 1998, 68(3): 355–362
5	Grinstaff M W. Designing hydrogel adhesives for corneal wound repair. Biomaterials, 2007, 28(35): 5205–5214
6	Rodriguez-Tenreiro C, Diez-Bueno L, Concheiro A, . Cyclodextrin/carbopol micro-scale interpenetrating networks (ms-IPNs) for drug delivery. Journal of Controlled Release, 2007, 123(1): 56–66
7	Schmedlen R H, Masters K S, West J L. Photocrosslinkable polyvinyl alcohol hydrogels that can be modified with cell adhesion peptides for use in tissue engineering. Biomaterials, 2002, 23(22): 4325–4332
8	Nie T, Baldwin A, Yamaguchi N, . Production of heparin-functionalized hydrogels for the development of responsive and controlled growth factor delivery systems. Journal of Controlled Release, 2007, 122(3): 287–296
9	Hwang A A, Lee B Y, Clemens D L, . pH-Responsive isoniazid-loaded nanoparticles markedly improve tuberculosis treatment in mice. Small, 2015, 11(38): 5066–5078
10	Heinrich T, Traulsen C H, Holzweber M, . Coupled molecular switching processes in ordered mono- and multilayers of stimulus-responsive rotaxanes on gold surfaces. Journal of the American Chemical Society, 2015, 137(13): 4382–4390
11	He X, Liu Z, Fan F, . Poly(ionic liquids) hollow nanospheres with PDMAEMA as joint support of highly dispersed gold nanoparticles for thermally adjustable catalysis. Journal of Nanoparticle Research, 2015, 17(2): 1–10
12	Xiao Z, Ji C, Shi J, . DNA self-assembly of targeted near-infrared-responsive gold nanoparticles for cancer thermo-chemotherapy. Angewandte Chemie, 2012, 51(47): 11853–11857
13	Chen T, Chang D P, Zhang J, . Manipulating the motion of gold aggregates using stimulus-responsive patterned polymer brushes as a motor. Advanced Functional Materials, 2012, 22(2): 429–434
14	Azzam T, Eisenberg A. Monolayer-protected gold nanoparticles by the self-assembly of micellar poly(ethylene oxide)-b-poly(ϵ-caprolactone) block copolymer. Langmuir, 2007, 23(4): 2126–2132
15	Shan J, Tenhu H. Recent advances in polymer protected gold nanoparticles: synthesis, properties and applications. Chemical Communications, 2007, (44): 4580–4598
16	Li J, Wu W, Han C, . Aggregation behavior of pH- and thermo-responsive block copolymer protected gold nanoparticles. Colloid & Polymer Science, 2014, 292(7): 1657–1664
17	Sharker S M, Lee J E, Kim S H, . pH triggered in vivo photothermal therapy and fluorescence nanoplatform of cancer based on responsive polymer-indocyanine green integrated reduced graphene oxide. Biomaterials, 2015, 61: 229–238
18	Wang F, Wang Y C, Dou S, . Doxorubicin-tethered responsive gold nanoparticles facilitate intracellular drug delivery for overcoming multidrug resistance in cancer cells. ACS Nano, 2011, 5(5): 3679–3692
19	Shim M S, Kwon Y J. Stimuli-responsive polymers and nanomaterials for gene delivery and imaging applications. Advanced Drug Delivery Reviews, 2012, 64(11): 1046–1059
20	Mecerreyes D. Polymeric ionic liquids: Broadening the properties and applications of polyelectrolytes. Progress in Polymer Science, 2011, 36(12): 1629–1648
21	Amajjahe S, Ritter H. Microwave-sensitive foamable poly(ionic liquids) bearing tert-butyl ester groups: influence of counterions on the ester pyrolysis. Macromolecular Rapid Communications, 2009, 30(2): 94–98
22	Mori H, Yahagi M, Endo T. RAFT polymerization of N-vinylimidazolium salts and synthesis of thermoresponsive ionic liquid block copolymers. Macromolecules, 2009, 42(21): 8082–8092
23	Vijayakrishna K, Mecerreyes D, Gnanou Y, . Polymeric vesicles and micelles obtained by self-assembly of ionic liquid-based block copolymers triggered by anion or solvent exchange. Macromolecules, 2009, 42(14): 5167–5174
24	Stancik C M, Lavoie A R, Schütz J, . Micelles of imidazolium-functionalized polystyrene diblock copolymers investigated with neutron and light scattering. Langmuir, 2004, 20(3): 596–605
25	Zhao D, Chen X, Liu Y, . Thermosensitive and pH-sensitive Au–Pd bimetallic nanocomposites. Journal of Colloid and Interface Science, 2009, 331(1): 104–112
26	Matsui J, Akamatsu K, Hara N, . SPR sensor chip for detection of small molecules using molecularly imprinted polymer with embedded gold nanoparticles. Analytical Chemistry, 2005, 77(13): 4282–4285
27	Li J, Liang J, Wu W, . AuCl4--responsive self-assembly of ionic liquid block copolymers for obtaining composite gold nanoparticles and polymeric micelles with controlled morphologies. New Journal of Chemistry, 2014, 38(6): 2508–2513
28	Washiro S, Yoshizawa M, Nakajima H, . Highly ion conductive flexible films composed of network polymers based on polymerizable ionic liquids. Polymer, 2004, 45(5): 1577–1582
29	Huang X, Xiao Y, Zhang W, . In-situ formation of silver nanoparticles stabilized by amphiphilic star-shaped copolymer and their catalytic application. Applied Surface Science, 2012, 258(7): 2655–2660
30	Li J B, Zhang S J, Liang J, . One-dimensional assembly of polymeric ionic liquid capped gold nanoparticles driven by electrostatic dipole interaction. RSC Advances, 2015, 5(11): 7994–8001
31	He J, Liu Y, Babu T, . Self-assembly of inorganic nanoparticle vesicles and tubules driven by tethered linear block copolymers. Journal of the American Chemical Society, 2012, 134(28): 11342–11345
32	Rakhmatullina E, Braun T, Chami M, . Self-organization behavior of methacrylate-based amphiphilic di- and triblock copolymers. Langmuir, 2007, 23(24): 12371–12379
33	Karjalainen E, Chenna N, Laurinmäki P, . Diblock copolymers consisting of a polymerized ionic liquid and poly(N-isopropylacrylamide). Effects of PNIPAM block length and counter ion on self-assembling and thermal properties. Polymer Chemistry, 2013, 4(4): 1014–1024
34	Mori H, Ebina Y, Kambara R, . Temperature-responsive self-assembly of star block copolymers with poly(ionic liquid) segments. Polymer Journal, 2012, 44(6): 550–560
35	Men Y, Schlaad H, Yuan J. Cationic poly(ionic liquid) with tunable lower critical solution temperature-type phase transition. ACS Macro Letters, 2013, 2(5): 456–459

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